KR20120040154A - Aluminum chelate latent curing agent - Google Patents

Abstract

Glycidyl ether type epoxy compounds can be hardened at a lower temperature than an aluminum chelate latent curing agent produced by emulsification / interface polymerization of polyfunctional isocyanate in the presence of a radical polymerizable monomer such as divinylbenzene and a radical polymerization initiator. A novel aluminum chelate latent curing agent is microencapsulated in a core shell form, in which an aluminum chelate curing agent and a cationic polymerizable compound are contained in a capsule comprising an interfacial polymer of a polyfunctional isocyanate.

Description

Aluminum chelate latent hardener {ALUMINUM CHELATE LATENT CURING AGENT}

The present invention relates to a core-shell microcapsule type aluminum chelate latent curing agent in which an aluminum chelate curing agent is contained in a capsule made of an interfacial polymer of polyfunctional isocyanate.

Conventionally, as a curing agent exhibiting low temperature fast curing activity to an epoxy resin, a microencapsulated aluminum chelate latent curing agent in which an aluminum chelating agent is maintained in a porous resin obtained by interfacial polymerization of a polyfunctional isocyanate compound has been proposed ( Patent document 1).

By the way, in the case of the thermosetting epoxy resin composition which mix | blended the epoxy compound and the aluminum chelate latent hardening | curing agent as disclosed in patent document 1 for hardening it, in order to activate a hardening | curing agent, the silanolate anion derived from a silane coupling agent Although the presence is required, the silanolate anion is added to the β-position carbon of the epoxy group of the epoxy compound and there is a problem that the polymerization stop reaction occurs. Therefore, the glycidyl ether-based epoxy compound that is likely to be β carbon addition reaction is polymerized. It was difficult to polymerize without causing a reaction. Therefore, although manufacturing cost is expensive, there exists a problem that the alicyclic epoxy compound which hardly produces an addition reaction to (beta) position carbon by a silanolate anion cannot be used.

For this reason, in order to make the glycidyl ether type epoxy compound low-temperature-fast-curing with the aluminum chelate latent hardener as disclosed in patent document 1, in a thermosetting epoxy resin composition, it is conventionally used as a silane coupling agent. When using a high-stereoscopic obstacle silanol compound which has a specific chemical structure which is not used in combination with an aluminum chelate latent curing agent, and interfacially polymerizes the polyfunctional isocyanate compound, radical polymerizable monomers such as divinylbenzene, etc. It is proposed to improve the mechanical properties of a porous microcapsule by coexisting and copolymerizing a radical polymerization initiator to increase the thermal response rate at the time of curing an epoxy compound (Patent Document 2).

Japanese Laid-Open Patent Publication 2006-70051 Japanese Unexamined Patent Publication No. 2009-197206

However, in the case of the thermosetting epoxy resin composition of Patent Literature 2 containing a porous microencapsulated aluminum chelate latent curing agent as disclosed in Patent Literature 1, the low-temperature fast curing property may be sufficient depending on the application. There was no demand to further improve low temperature fast curing. Moreover, since the radical polymerization reaction of radically polymerizable monomers, such as divinylbenzene, arises in the case of an emulsion-surface polymerization reaction at the time of manufacturing a latent hardening | curing agent, an unreacted radically polymerizable monomer is carried out to a porous microcapsule. It may remain. The remaining of such unreacted radically polymerizable monomers as impurities may affect the performance of the cured product.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems of the prior art, and is an aluminum chelate latent curing agent prepared by emulsification / interface polymerization of a polyfunctional isocyanate in the presence of a radical polymerizable monomer such as divinylbenzene and a radical polymerization initiator. Furthermore, it is providing the novel aluminum chelate latent hardener which can quick-cure a glycidyl-type epoxy compound at low temperature.

MEANS TO SOLVE THE PROBLEM This inventor does not microencapsulate an aluminum chelate hardening | curing agent into a porous type, but encloses an aluminum chelate hardening | curing agent with a cation polymeric compound in the capsule which consists of an interfacial polymer of polyfunctional isocyanate, and microencapsulates in a core-shell type It was found that the above-described objects can be achieved, and the present invention has been completed.

That is, the present invention is an aluminum chelate latent curing agent microencapsulated in a core-shell type, and an aluminum chelate latent curing agent in which an aluminum chelate curing agent and a cationic polymerizable compound are contained in a capsule made of an interfacial polymer of polyfunctional isocyanate. To provide.

Moreover, this invention is a manufacturing method of the aluminum chelate latent hardening | curing agent microencapsulated to the core-shell type mentioned above, Comprising: The oil phase which melt | dissolved the polyfunctional isocyanate and a cationically polymerizable compound in the volatile organic solvent, It emulsifies in the water phase containing a dispersing agent and surfactant, surface-polymerizes polyfunctional isocyanate, maintaining the emulsion state, and an aluminum chelate hardening | curing agent and a cation polymeric compound consist of an interfacial polymer of polyfunctional isocyanate. It provides a manufacturing method characterized in that it is enclosed in a capsule.

Moreover, this invention provides the thermosetting epoxy resin composition characterized by containing the above-mentioned aluminum chelate latent hardening | curing agent, a glycidyl ether type epoxy compound, and the silanol compound represented by Formula (A).

(Ar) _m Si (OH) _n (A)

In formula (A), m is 2 or 3, provided that the sum of m and n is 4. Ar is an aryl group which may be substituted.

The aluminum chelate latent curing agent of the present invention is a core-shell microcapsule containing an aluminum chelate curing agent in a capsule made of an interfacial polymer of polyfunctional isocyanate together with a cation polymerizable compound. Since the silanol compound does not exist in a microcapsule, an aluminum type hardening | curing agent and a cation polymeric compound do not react. In the thermosetting epoxy resin composition obtained by mixing a silanol compound and a glycidyl epoxy compound with the aluminum chelate latent curing agent of the present invention, if the microcapsule wall of the aluminum chelate latent curing agent is destroyed by pressure or heat, The active species produced by the reaction between the aluminum chelate curing agent and the cationic polymerizable compound with the silanol compound can cationic polymerize the glycidyl ether type epoxy compound.

1 is an electron micrograph of an aluminum chelate latent curing agent of Example 2. FIG.
2 is an electron micrograph of the aluminum chelate latent curing agent of Example 2. FIG.
3 is a purge trap GC / MS chart of the aluminum chelate latent curing agent of Example 2. FIG.
4 is a DSC chart of the thermosetting epoxy resin compositions of Example 1, Example 2, and Comparative Example 1. FIG.
5 is an electron micrograph of the aluminum chelate latent curing agent of Example 3. FIG.
6 is an electron micrograph of the aluminum chelate latent curing agent of Example 3. FIG.
7 is a purge trap GC / MS chart of the aluminum chelate latent curing agent of Example 3. FIG.
8 is a DSC chart of the thermosetting epoxy resin compositions of Examples 2 and 3. FIG.
9 is an electron micrograph of the aluminum chelate latent curing agent of Example 4. FIG.
10 is an electron micrograph of the aluminum chelate latent curing agent of Example 4. FIG.
11 is a DSC chart of the thermosetting epoxy resin compositions of Examples 3, 4 and 5.
12 is a DSC chart of the thermosetting epoxy resin compositions of Examples 3 and 6. FIG.
FIG. 13 is a DSC chart of the thermosetting epoxy resin compositions of Examples 2, 3, 7 and Comparative Example 2. FIG.
14 is a DSC chart of the thermosetting epoxy resin compositions of Examples 3 and Comparative Examples 3 and 4. FIG.

The aluminum chelate latent curing agent microencapsulated in the core-shell type of the present invention is contained in a capsule in which the aluminum chelate curing agent and the cationic polymerizable compound are composed of an interfacial polymer of polyfunctional isocyanate. For this reason, control of hardening temperature becomes easy by adjusting the thickness of a shell layer. Moreover, the application to the pressure-sensitive adhesive accompanying the destruction of the shell can be expected.

Since this aluminum chelate latent curing agent is produced using an emulsion-surface polymerization method, the shape is spherical, and the particle diameter thereof is preferably 0.1? In terms of curability and dispersibility. 50 micrometers, More preferably, it is 0.1? 10 μm.

Moreover, when the crosslinking degree of the capsule wall which consists of an interfacial polymer of polyfunctional isocyanate is too small, the latent hardening agent of aluminum chelate type hardening | curing agent will fall, and when too large, the thermal responsiveness will fall, and according to a use purpose, It is preferable to adjust the crosslinking degree. Here, the crosslinking degree of a capsule wall can be measured by a micro compression test.

It is preferable that an aluminum chelate latent curing agent does not substantially contain the organic solvent used at the time of the interfacial polymerization, specifically, 1 ppm or less from the viewpoint of curing stability.

<Aluminum chelate curing agent>

As the aluminum chelate curing agent constituting the core of the aluminum chelate latent curing agent microencapsulated into the core-shell type of the present invention, a complex compound in which three β-ketoenolate anions represented by Formula (1) is coordinated with aluminum Can be mentioned.

Here, R ¹ , R ² and R ³ are each independently an alkyl group or an alkoxyl group. A methyl group, an ethyl group, etc. are mentioned as an alkyl group. As an alkoxyl group, a methoxy group, an ethoxy group, an oleyloxy group, etc. are mentioned.

Specific examples of the aluminum chelating agent represented by formula (1) include aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), and aluminum monoacetylacetonate bisole One acetoacetate, ethyl acetoacetate aluminum diisopropylate, alkyl acetoacetate aluminum diisopropylate, and the like.

<Cationically polymerizable compound>

The cationically polymerizable compound contained in the microcapsules together with the aluminum chelate curing agent is activated by an external silanol compound when the microcapsule is broken, and rapidly cationic polymerization with the aluminum chelate curing agent. Therefore, by containing such a cationically polymerizable compound together with the aluminum chelate curing agent in a microcapsule, the low temperature fast curing property of the aluminum chelate latent curing agent can be improved.

As such a cationically polymerizable compound, a cyclic ether compound is preferably mentioned from the viewpoint of low temperature fast curing. Especially, it is preferable that it is liquid at room temperature from the viewpoint of compatibility and fluidity with an aluminum chelating agent. As such a cyclic ether type compound, a polyfunctional glycidyl ether type epoxy compound, an alicyclic epoxy compound, and an oxetane compound are mentioned preferably. In these, a polyfunctional alicyclic epoxy compound and an oxetane compound can be used preferably. These cationic polymerizable compounds may be used independently, respectively and may be used together. When using an alicyclic epoxy compound and an oxetane compound together, with respect to 100 mass parts of electrons, Preferably the latter is 10? 100 parts by mass is used. Moreover, 2 or more types of cationically polymerizable compounds can also be mixed and used.

Moreover, since polyfunctional olefin compounds, such as divinylbenzene, are radically polymerizable, it does not need to apply to this invention. Therefore, it is not necessary to consider the adverse effect by the remainder of a radically polymerizable compound after interfacial polymerization.

Preferable examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Suracure UVR-6110 (Union-Carbide Co., Ltd.): Celoxide 2021P (Diecel Chemistry) Industrial Co., Ltd.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (ERL-4206 (manufactured by Union Carbide)), limonene dioxide (Celoxide 3000 (Dicel Chemical Industries, Ltd.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3 , 4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (Sairacure UVR-6128 (manufactured by Union Carbide)), bis (3,4-epoxycyclohexyl) Methyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxy And the like claw hexyl) diethyl siloxane.

Preferable specific examples of the oxetane compound include bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3 -Oxetanyl) methoxy] methyl} benzene, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylic acid bis [(3 -Ethyl-3-oxetanyl)] methyl ester, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- {[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane, phenol novolak oxetane, etc. are mentioned.

When the amount of the cationic polymerizable compound described above used for the aluminum chelate curing agent is too small, the curing activity decreases, and if the amount is too large, the curing temperature tends to be high, so it is preferably 100 parts by mass of the aluminum chelate curing agent. 10? 300 parts by mass, more preferably 10? 100 parts by mass.

<Polyfunctional isocyanate compound>

The polyfunctional isocyanate compound constituting the microcapsule wall is preferably a compound having two or more isocyanate groups, preferably three isocyanate groups in one molecule. As a more preferable example of such a trifunctional isocyanate compound, TMP adduct body of Formula (2) which made 3 mol of diisocyanate compounds react with 1 mol of trimethylol propanes, and 3 mol of diisocyanate compounds self-condensed of Formula (3) The biuret body of Formula (4) which the other 1 mol of diisocyanate condensed to the diisocyanate urea obtained from 2 mol of isocyanurate body and 3 mol of diisocyanate compounds is mentioned.

(2) above? In (4), substituent R is a part except the isocyanate group of a diisocyanate compound. Specific examples of such diisocyanate compounds include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-xylylene diisocyanate, hexamethylene diisocyanate, hexahydro-m-xylylene diisocyanate, iso Poron diisocyanate, 4,4'- methylene diphenyl diisocyanate, etc. are mentioned.

In the capsule wall obtained by interfacial polymerization of such a polyfunctional isocyanate compound (capsule wall of the core cell type capsule), a part of the isocyanate group undergoes hydrolysis during the interfacial polymerization to become an amino group, and the amino group and the isocyanate group react to form urea bonds. To polymerize. When the aluminum chelate latent curing agent having such a capsule wall is heated for curing, the molecular chain of the capsule polymerization wall is loosened, and the contained aluminum chelate curing agent and the cationically polymerizable compound are the outside of the latent curing agent. It becomes possible to contact with the silanol compound of Formula (A) and glycidyl ether-type epoxy compound which are mentioned later, and can advance hardening reaction.

Moreover, when the crosslinking degree of the capsule wall which consists of an interfacial polymer of polyfunctional isocyanate is too small, since the latent potential of an aluminum chelate latent hardening | curing agent will fall, if it is too large, there exists a tendency for the thermal responsiveness to fall, according to the use purpose, It is preferable to adjust the degree of crosslinking. Here, the crosslinking degree of a capsule wall can be measured by a micro compression test.

In addition, the total amount of the aluminum chelate-based curing agent and the cationic polymerizable compound contained in the capsule wall in the aluminum chelate-based latent curing agent decreases the thermal responsiveness if the total amount is too small, and the latent potential decreases if the amount is too large. In 100 parts by mass of the capsule wall made of the interfacial polymer of polyfunctional isocyanate, the total amount of the aluminum chelate curing agent and the cation polymerizable compound is preferably 100? 2000 parts by mass, more preferably 100? Contains 1000 parts by mass.

Moreover, you may perform the impregnation process of the aluminum chelate-type hardening | curing agent solution with respect to a capsule wall, in order to improve the low temperature fast hardening property of an aluminum chelate-type latent hardening | curing agent. In the impregnation method, the aluminum chelate latent curing agent is dispersed in an organic solvent (for example, ethanol), and the aluminum chelate curing agent (for example, monoacetylacetonate bis (ethylacetoacetate)) is dispersed in the dispersion. Isopropanol solution) was added, and room temperature? How many hours at a temperature of about 50 ℃? The method of continuing stirring overnight is mentioned.

<Method for producing aluminum chelate latent curing agent>

The aluminum chelate latent curing agent microencapsulated in the core-shell type of the present invention emulsifies an oil phase obtained by dissolving a polyfunctional isocyanate and a cationic polymerizable compound in a volatile organic solvent in an aqueous phase containing water, a dispersant, and a surfactant, The polyfunctional isocyanate can be interfacially polymerized while maintaining the emulsified state, and the aluminum chelate curing agent and the cationic polymerizable compound can be produced by encapsulating in a capsule made of the interfacial polymer of the polyfunctional isocyanate. It demonstrates in detail below.

In this production method, first, an aluminum chelate curing agent, a polyfunctional isocyanate compound, and a cationic polymerizable compound are dissolved in a volatile organic solvent to prepare a solution that becomes an oil phase in interfacial polymerization. Here, the reason for using a volatile organic solvent is as follows. That is, in the case where a high boiling point solvent having a boiling point of more than 300 ° C., such as that used by a conventional interfacial polymerization method, is used, since the organic solvent does not volatilize during interfacial polymerization, the contact probability with isocyanate-water does not increase, and This is because the degree of progress of interfacial polymerization in between becomes insufficient. Therefore, even if it is interfacially polymerized, it is difficult to obtain a polymer having a good shape retention, and even when obtained, the polymer has a high boiling point solvent as it is, and the high boiling point solvent is a thermosetting type when blended with the thermosetting resin composition. This is because it adversely affects the physical properties of the cured product of the resin composition. For this reason, in this manufacturing method, what is volatile is used as an organic solvent used when preparing an oil phase.

As such a volatile organic solvent, as a good solvent (an each solubility of 0.1 g / mL (organic solvent) or more) with respect to an aluminum chelate type hardening | curing agent, a polyfunctional isocyanate compound, and a cationic polymerizable compound, It is preferable that the water boiling point is not substantially dissolved (water solubility is 0.5 g / ml (organic solvent) or less) and the boiling point under atmospheric pressure is 100 ° C or lower. Specific examples of such volatile organic solvents include alcohols, acetate esters, ketones, and the like. Among them, ethyl acetate is preferred in view of high polarity, low boiling point and poor water solubility.

If the amount of the volatile organic solvent is too small, the potential decreases when the amount is too small, based on 100 parts by mass of the total amount of the aluminum chelate-based curing agent, the polyfunctional isocyanate compound, and the cationic polymerizable compound. Since property falls, Preferably it is 1? 50 parts by mass, more preferably 1? 30 parts by mass. Moreover, this compounding range became relatively smaller than the usage-amount at the time of manufacture of the conventional porous type aluminum chelate latent hardening | curing agent. For this reason, since the usage-amount of an organic solvent can be reduced, environmental load can be made smaller than before.

In addition, although the viscosity of the solution which becomes an oil phase can be reduced by using the usage-amount of a volatile organic solvent relatively large in the usage-amount of a volatile organic solvent, since stirring efficiency improves when lowering a viscosity, in a reaction system, It becomes possible to refine and uniformize the oil phase more, and the resulting latent curing agent particle diameter is submicron? It is possible to make the particle size distribution monodisperse while controlling to the magnitude of several microns. The viscosity of the solution to be oil phase is 1? It is preferable to set it to 300 mPa? S.

When dissolving an aluminum chelate hardening | curing agent, a polyfunctional isocyanate compound, and a cationically polymerizable compound in a volatile organic solvent, only stirring and stirring at room temperature under atmospheric pressure may be carried out as needed.

Next, in this manufacturing method, the oily solution in which the aluminum chelate-based curing agent, the polyfunctional isocyanate compound, and the cationic polymerizable compound are dissolved in the volatile organic solvent is added to an aqueous phase containing a dispersing agent to emulsify the emulsion state. Interfacial polymerization while maintaining. Here, as a dispersing agent, what is used in normal interfacial polymerization methods, such as polyvinyl alcohol, carboxymethylcellulose, gelatin, can be used. The amount of dispersant used is usually 0.1? 10.0 mass%.

The blending amount of the oil phase solution with respect to the water phase is polydispersed when the oil phase solution is too small. When the amount is excessively large, aggregation occurs due to miniaturization. 50 parts by mass.

As the emulsion and interfacial polymerization conditions, the size of the oil phase is preferably 1? Under stirring conditions (stirrer homogenizer; stirring speed 8000 rpm or more) which become 30 micrometers, it is normal under atmospheric pressure and the temperature of 30? 80 degreeC (preferably 50-80 degreeC), stirring time 2? The conditions to heat and stir for 12 hours are mentioned.

When PVA is used to emulsify and disperse the polyfunctional isocyanate compound, since the hydroxyl group of the PVA and the polyfunctional isocyanate compound react, the by-product adheres around the latent curing agent particles as foreign matter, and the particle shape itself Mold release. In order to prevent this phenomenon, what promotes the reactivity of a polyfunctional isocyanate compound and water, or suppresses the reactivity of a polyfunctional isocyanate compound and PVA is mentioned.

In order to promote the reactivity of the polyfunctional isocyanate compound and water, the blending amount of the aluminum chelate curing agent is preferably 1/2 or less, more preferably 1/3 or less, in terms of the mass of the polyfunctional isocyanate compound. Thereby, the probability that a polyfunctional isocyanate compound and water will contact will become high, and it will become easy to react with a polyfunctional isocyanate compound and water before PVA contacts an oily surface.

Moreover, in order to suppress the reactivity of a polyfunctional isocyanate compound and PVA, the compounding quantity of the aluminum chelate type hardening | curing agent in oil phase is mentioned. Specifically, the blending amount of the aluminum chelate-based curing agent is preferably equal to or larger than the mass of the polyfunctional isocyanate compound, more preferably 1.0? 2.0 times. Thereby, the isocyanate concentration in oily surface falls. In addition, since the polyfunctional isocyanate compound has a faster reaction (interface polymerization) rate with the amine formed by hydrolysis than a hydroxyl group, the reaction probability of the polyfunctional isocyanate compound and PVA can be reduced.

After completion of the interfacial polymerization, the polymer microparticles are separated by filtration and naturally dried to obtain the aluminum chelate latent curing agent of the present invention. Here, the hardening characteristic of an aluminum chelate latent hardener can be controlled by changing the kind and usage-amount of a polyfunctional isocyanate compound, the kind and usage-amount of an aluminum chelating agent, and interfacial polymerization conditions. For example, when the polymerization temperature is lowered, the curing temperature can be lowered. On the contrary, when the polymerization temperature is higher, the curing temperature can be increased.

<Thermosetting epoxy resin composition>

Next, the thermosetting epoxy resin composition containing the aluminum chelate latent curing agent of the present invention will be described.

In addition to the aluminum chelate latent curing agent of the present invention, the thermosetting epoxy resin composition further contains a silanol compound having relatively high steric hindrance and a glycidyl ether type epoxy resin. Therefore, in this thermosetting epoxy resin composition, a glycidyl ether type epoxy resin can be thermally polymerized without generating a polymerization terminating reaction.

If the content of the aluminum chelate latent curing agent in the thermosetting epoxy resin composition is too small, it will not be cured sufficiently. If too large, the resin properties (eg, flexibility) of the cured product of the composition will be lowered. 1? With respect to 100 parts by mass of the ether type epoxy resin composition. 70 parts by mass, preferably 1? 50 parts by mass.

The silanol compound mix | blended with the thermosetting epoxy resin composition of this invention differs from the conventional silane coupling agent which has a trialkoxy group, and is an aryl silanol which has a chemical structure of the following formula (A).

(Ar) _m Si (OH) _n (A)

Wherein m is 2 or 3, provided that the sum of m and n is 4; Therefore, the silanol compound of Formula (A) becomes a mono or a diol body. "Ar" is an aryl group which may be substituted. Examples of the aryl group include phenyl group, naphthyl group, anthracenyl group, azulenyl group, fluorenyl group, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyridyl group and the like. Can be mentioned. Especially, a phenyl group is preferable from a viewpoint of availability and acquisition cost. Although m pieces of Ar may be all the same or different, the same thing is preferable at the point of availability.

These aryl groups are 1? It may have three substituents, For example, Halogen, such as chloro and bromo; Trifluoromethyl; Nitro; Sulfo; Alkoxycarbonyl, such as carboxyl, methoxycarbonyl, ethoxycarbonyl; Formyl, etc. Electron donating groups, such as an electron withdrawing group, alkyl such as methyl, ethyl, propyl; alkoxy such as methoxy and ethoxy; hydroxy; amino; monoalkylamino such as monomethylamino; dialkylamino such as dimethylamino Can be mentioned. In addition, since the acidity of the hydroxyl group of silanol can be raised by using an electron withdrawing group as a substituent, the acidity can be reduced by using an electron donating group, and control of hardening activity becomes possible. Here, although m substituents may differ for every m Ar, it is preferable that m substituents are the same from the point of availability. Moreover, only some Ar may have a substituent and other Ar may not have a substituent.

Also in the silanol compound of Formula (A), a triphenyl silanol or a diphenyl silanol is mentioned as a preferable thing. Especially preferred is triphenylsilanol.

In the thermosetting epoxy resin composition of this invention, with respect to content of the silanol compound of Formula (A), the content rate of the said silanol compound with respect to the sum total of a silanol compound and glycidyl ether type epoxy resin is too much. If it is small, hardening becomes insufficient, and if too large, resin characteristics (flexibility, etc.) will fall, Preferably it is 5? 30 mass%, More preferably, it is 5? 20 mass%.

The glycidyl ether type epoxy compound which comprises the thermosetting epoxy resin composition of this invention is used as a film formation component. As such glycidyl ether type epoxy resin, a liquid may be sufficient and solid may be sufficient, and epoxy equivalent is usually 100? As about 4000, it is preferable to have two or more epoxy groups in a molecule | numerator. For example, a bisphenol A epoxy compound, a bisphenol F epoxy compound, a phenol novolak-type epoxy compound, a cresol novolak-type epoxy compound, an ester type epoxy compound, etc. are mentioned. Especially, a bisphenol-A epoxy compound and a bisphenol-F epoxy compound can be used preferably from a resin characteristic point. Moreover, these epoxy compounds also contain a monomer, an oligomer, and a polymer. You may use these 2 or more types of epoxy compounds in mixture.

The thermosetting epoxy resin composition of this invention can use together the alicyclic epoxy compound and oxetane compound which are illustrated as a cationically polymerizable compound contained in a capsule other than a glycidyl ether type epoxy compound as a resin component. When using an oxetane compound, the usage-amount becomes like this. Preferably it is 10? 100 parts by mass, more preferably 20? 70 parts by mass.

The thermosetting epoxy resin composition of this invention can also contain a silane coupling agent, fillers, such as a silica and a mica, a pigment, an antistatic agent, etc. separately from the silanol compound of Formula (1) as needed.

The silane coupling agent is Paragraph 0007 of Unexamined-Japanese-Patent No. 2002-212537? As described in 0010, it has a function of working with an aluminum chelating agent to initiate cationic polymerization of a thermosetting resin (eg, a thermosetting epoxy resin). Therefore, the effect of promoting hardening of an epoxy resin is acquired by using a small amount together of such a silane coupling agent. As such a silane coupling agent, it is 1? In a molecule. Having a lower alkoxy group of 3, a group having a reactivity to the functional group of the thermosetting resin in the molecule, for example, vinyl group, styryl group, acryloyloxy group, methacryloyloxy group, epoxy group, amino group, mercapto group and the like You may have Moreover, since the latent hardening | curing agent of this invention is a cation-type hardening | curing agent, the coupling agent which has an amino group and a mercapto group can be used when an amino group and a mercapto group do not substantially capture the generated cation species.

Specific examples of such a silane coupling agent include vinyl tris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-styryltrimethoxysilane, and γ-methacryloxypropyl. Trimethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Diethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N -Phenyl- (gamma)-aminopropyl trimethoxysilane, (gamma)-mercaptopropyl trimethoxysilane, (gamma)-chloropropyl trimethoxysilane, etc. are mentioned.

When using a small amount of silane coupling agents together, when the content is too small, an addition effect cannot be expected, and when too large, the effect of the polymerization terminating reaction by the silanolate anion which arises from a silane coupling agent will generate | occur | produce aluminum, 1? Per 100 parts by mass of chelate latent curing agent 300 parts by mass, preferably 1? 100 parts by mass.

<Preparation of a thermosetting epoxy resin composition>

The thermosetting epoxy resin composition of the present invention is obtained by uniformly mixing and stirring an aluminum chelate latent curing agent, a silanol compound of formula (A) and a glycidyl ether type epoxy compound, and, if necessary, additives according to a conventional method. It can manufacture.

The thermosetting epoxy resin composition of the present invention thus obtained uses an aluminum chelate-based latent curing agent as a curing agent, and thus is excellent in storage stability despite being one formulation. Moreover, although it contains the glycidyl ether type epoxy compound which could not fully harden with an aluminum chelate latent hardening | curing agent, since it contains specific silanol of a high-stereoscopic obstacle, a thermosetting type epoxy resin composition is made into a low temperature rapid hardening. Cationic polymerization can be carried out.

<Anisotropic Conductive Adhesive>

An anisotropic conductive adhesive is mentioned as a useful use of the thermosetting epoxy resin composition of this invention. Such an anisotropic electrically conductive adhesive is what disperse | distributed electroconductive particle to the thermosetting epoxy resin composition, and is used as a paste or shape | molding in a film. As the conductive particles, metal particles such as nickel, cobalt, silver, copper, gold, palladium and the like, which are conventionally used as conductive particles of an anisotropic conductive adhesive, can be used. These can use 2 or more types together and can also make particle size and a compounding quantity the same structure as before. A filler, a softener, an accelerator, an anti-aging agent, a coloring agent (pigment, dye), an organic solvent, an ion catcher agent, etc. can be mix | blended with such an anisotropic electrically conductive adhesive as needed.

Example

Hereinafter, the present invention will be described in detail.

Example 1 (In the case of containing an alicyclic epoxy compound)

3 liters with 800 parts by mass of distilled water, 0.05 parts by mass of surfactant (Neulex R, Nichiyu Co., Ltd.), and 4 parts by mass of polyvinyl alcohol (PVA-205, Kuraray Co., Ltd.) as a dispersant. Into the interfacial polymerization vessel of and mixed uniformly. In addition to this mixture, 100 parts by mass of a 24% isopropanol solution (aluminum chelate D, Kawaken Fine Chemical Co., Ltd.) of aluminum monoacetylacetonate bis (ethylacetoacetate) as an aluminum chelate curing agent, and a polyfunctional isocyanate 70 mass parts of trimethylolpropane (1 mol) adducts of methylenediphenyl-4,4'- diisocyanate (3 mol) (D-109, Mitsui Chemical Co., Ltd.), and 3, 4- as alicyclic epoxy compound An oily solution obtained by dissolving 70 parts by mass of epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P, Daicel Chemical Industry Co., Ltd.) in 30 parts by mass of ethyl acetate as a volatile organic solvent was added thereto. Emulsion mixing was carried out by a homogenizer (T-50, IKA Japan Co., Ltd .; emulsification condition 10000 rpm / 5 minutes), and the surface polymerization was carried out at 80 ° C for 6 hours.

After completion | finish of reaction, the polymerization reaction liquid was left to cool to room temperature, the interfacial polymerization particle was separated by filtration by filtration, and the mass was obtained by air-drying. This mass was pulverized using a disintegration apparatus (AO-JET MILL, Seishin Co., Ltd.) to obtain an aluminum chelate latent curing agent encapsulated in a spherical core shell having an average particle diameter of 5 µm.

By mixing uniformly 4 parts by mass of the obtained aluminum chelate latent curing agent, 8 parts by mass of triphenylsilanol (Tokyo Chemical Industry Co., Ltd.), and 80 parts by mass of bisphenol A type epoxy resin (EP828, Mitsubishi Chemical Corporation) The thermosetting epoxy resin composition of Example 1 was prepared. In addition, the thing which melt | dissolved by heating at 80 degreeC for 2 hours was used for the triphenyl silanol in bisphenol-A epoxy resin.

Example 2 (In the case of containing an alicyclic epoxy compound)

The amount of the trimethylolpropane (1 mol) adduct (D-109, Mitsui Chemical Co., Ltd.) of methylenediphenyl-4,4'-diisocyanate (3 mol) which is a polyfunctional isocyanate is 70 mass parts to 50 mass parts Except for changing, the same treatment as in Example 1 was repeated to obtain an aluminum chelate latent curing agent microencapsulated into a spherical core shell of a volume average particle diameter of 5 µm. In addition, a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

Electron micrographs of the aluminum chelate latent curing agent of Example 2 are shown in Figs. 1 (x1000) and 2 (x12000). These micrographs show that the aluminum chelate latent curing agent of Example 2 is a spherical core-shell microcapsule.

<Detection of Cationic Polymeric Compounds in Capsules by Purge Trap GC / MS>

The purge trap chart of the aluminum chelate latent hardener of Example 2 is shown in FIG. At the position of 15.084 minutes in this chart, the peak intrinsic to ceoxide 2021P was detected. Therefore, it was confirmed that the cationically polymerizable compound contained in the capsule leaked out of the capsule by heating.

In addition, the purge trap was performed on the conditions of 15 minutes of heating at 120 degreeC using the gas chromatograph mass spectrometer provided with a capillary column (HP6890 / 5973 MS (Agilent)).

Comparative Example 1 (when divinylbenzene / radical polymerization initiator is included)

100 parts by mass of a 24% isopropanol solution (aluminum chelate D, Kawaken Fine Chemical Co., Ltd.) of aluminum monoacetylacetonate bis (ethylacetoacetate) as an oil phase solution, and methylenediphenyl-4,4'-diisocyanate (3 Mol) trimethylolpropane (1 mol) adduct (D-109, Mitsui Chemical Co., Ltd.) 70 parts by mass, 30 parts by mass of divinylbenzene, and a radical polymerization initiator (faroyl L, Nichi Oil Co., Ltd.) Except for using the solution which melt | dissolved 0.3 mass part in 100 mass parts of ethyl acetate, the aluminum chelate in which the aluminum chelate-type hardening | curing agent is hold | maintained in spherical porous resin of 3 micrometers of volume average particle diameters is repeated by repeating the process similar to Example 1. System latent curing agents were obtained. In addition, a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

<Evaluation of Examples 1 and 2 and Comparative Example 1>

The obtained thermosetting epoxy resin composition was thermally analyzed using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments). The obtained result is shown in Table 1 and FIG. Here, with regard to the curing characteristics of the aluminum chelate latent curing agent, the exothermic onset temperature means the curing initiation temperature, the exothermic peak temperature means the temperature at which curing is most active, and the exothermic end temperature is the curing end temperature. And peak area means total calorific value.

As can be seen from Table 1 and Fig. 4, the thermosetting type of Examples 1 and 2 using an aluminum chelate latent curing agent encapsulated with an aluminum chelate curing agent and an alicyclic epoxy compound in an emulsion-interface polymerized product of polyfunctional isocyanate. In the case of the epoxy resin composition, compared with the thermosetting epoxy resin composition of the comparative example 1 which does not microencapsulate a cationically polymerizable compound with polyfunctional isocyanate, and contains the hardening agent which radically superposed | polymerized divinylbenzene at the time of interfacial polymerization, It was possible to lower the exothermic peak temperature by about 15 ° C. and the exothermic onset temperature by about 20 ° C.

In addition, since the exothermic onset temperature exceeded 70 degreeC, the thermosetting epoxy resin compositions of Examples 1 and 2 were excellent in storage property at room temperature, and also had the potential as a hardening | curing agent.

In the case of the aluminum chelate-based curing agent and the thermosetting epoxy resin composition obtained by repeating the same operation as in Comparative Example 1 except that divinylbenzene and the radical polymerization initiator were not used together, the exothermic onset temperature was higher than in the case of Comparative Example 1 Since the exothermic peak temperature has shifted to the high temperature side of about 20 ° C, it is added here that there is a problem in low temperature fast curing.

Example 3 (In the case of containing oxetane compound)

Oxetane compound (di [1-ethyl (3-oxetanyl)] methyl ether (OXT-221) instead of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate which is an alicyclic epoxy compound Except for using Toa synthesis Co., Ltd.), the operation of Example 2 was repeated, and the aluminum chelate latent hardening | curing agent microencapsulated in the spherical core-shell shape of volume-average average particle diameter of 5 micrometers was obtained. In addition, a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

Electron micrographs of the aluminum chelate latent curing agent of Example 3 are shown in Figs. 5 (x2000) and 6 (x15000). These micrographs show that the aluminum chelate latent curing agent of Example 3 is a spherical core-shell microcapsule.

<Detection of Cationic Polymeric Compounds in Capsules by Purge Trap GC / MS>

The purge trap chart of the aluminum chelate latent hardener of Example 3 is shown in FIG. At the position of 12.859 minutes in this chart, the peak inherent in OXT-221 was detected. Therefore, it was confirmed that the cationically polymerizable compound contained in the capsule leaked out of the capsule by heating.

In addition, the purge trap is the same as that of the Example 2. FIG.

<Evaluation of Example 3>

The obtained thermosetting epoxy resin composition was thermally analyzed using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments). The obtained result is shown in Table 2 and FIG. For comparison, the result of Example 2 is also written together.

It can be seen from Table 2 and FIG. 8 that the exothermic peak is sharper and the fast curing property is improved by using the oxetane compound instead of the alicyclic epoxy compound.

Example 4 (In the case of containing oxetane compound)

Except having changed the compounding quantity of polyfunctional isocyanate from 50 mass part to 40 mass part, the aluminum chelate type | system | group encapsulated microscopically in spherical core-shell shape of the volume conversion average particle diameter of 5 micrometers of Example 4 by repeating operation of Example 3 A sex hardener was obtained. In addition, a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

Electron micrographs of the aluminum chelate latent curing agent of Example 4 are shown in Figs. 9 (x2000) and 10 (x15000). From these micrographs, it can be seen that the aluminum chelate latent curing agent of Example 4 is a spherical core-shell microcapsule.

Example 5 (Including Oxetane Compound)

Except having changed the compounding quantity of polyfunctional isocyanate from 50 mass part to 30 mass part, the aluminum chelate type | system | group encapsulated micro-encapsulated in the spherical core-shell shape of the volume conversion average particle diameter of 5 micrometers of Example 5 by repeating operation of Example 3 A sex hardener was obtained. In addition, a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

<Evaluation of Examples 4 and 5>

The obtained thermosetting epoxy resin composition was thermally analyzed using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments). The obtained result is shown in Table 3 and FIG. For comparison, the result of Example 3 is also written together.

As can be seen from the results in Table 3 and FIG. 11, the exothermic peak temperature was shifted to the low temperature side by reducing the compounding amount of the polyfunctional isocyanate. In addition, the case of Example 4 showed the largest exothermic total amount.

Example 6 (In the case of containing oxetane compound and impregnation treatment of aluminum chelate curing agent)

10 parts by mass of the aluminum chelate latent curing agent obtained in Example 3, 40 parts by mass of a 24% isopropanol solution of aluminum monoacetylacetonate bis (ethylacetoacetate) (aluminum chelate D, Kawaken Fine Chemical Co., Ltd.) and ethanol 60 After adding to a mass part of mixed liquid, and stirring was continued at 30 degreeC for 6 hours, it filtered and washed with cyclohexane, and vacuum-dried (60 degreeC, 4 hours), The aluminum chelate latent impregnated with the aluminum chelate-type hardening | curing agent A curing agent was obtained. In addition, a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

<Evaluation of Example 6>

The obtained thermosetting epoxy resin composition was thermally analyzed using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments). The obtained result is shown in Table 4 and FIG. For comparison, the result of Example 3 is also written together.

From the results of Table 4 and FIG. 12, it can be seen that when the aluminum chelate curing agent is impregnated to the capsule wall of the microcapsules, the exothermic peak temperature can be shifted to the low temperature side, thereby improving low temperature curability. Also in this case, since the exothermic onset temperature is about 70 ° C., it can be seen that the room temperature storage stability is excellent.

Example 7 (Including Glycidyl Ether Type Epoxy Compound)

Example 2 other than using 50 parts by mass of trimethylolpropaneglycidyl ether (Epolite 100 MF, Kyoeisha Chemical Co., Ltd.) as a glycidyl ether type epoxy compound instead of 50 parts by mass of an alicyclic epoxy compound. By repeating the operation, an aluminum chelate latent curing agent microencapsulated in a spherical core shell of a volume-average average particle diameter of 5 μm was obtained. In addition, a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

Comparative Example 2 (In the case of containing a high boiling point lipophilic solvent)

The volume of the comparative example 2 was repeated by repeating operation of Example 2 except having used 50 mass parts of dibenzyltoluene (B-18, Matsumura Petroleum Co., Ltd.) of boiling point 390 degreeC instead of 50 mass parts of alicyclic epoxy compounds. An aluminum chelate latent curing agent microencapsulated in a spherical core-shell shape having an average particle diameter of 5 µm was obtained, and a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

<Evaluation of Example 7 and Comparative Example 2>

The obtained thermosetting epoxy resin composition was thermally analyzed using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments). The obtained result is shown in Table 5 and FIG. For comparison, the results of Examples 2 and 3 are also written together.

From the results of Table 5 and FIG. 13, the Example 7 in which the glycidyl ether type epoxy compound was contained in the microcapsules was compared with those in Examples 2 and 3 in which the alicyclic epoxy compound or the oxetane compound was contained in the capsule. The potential (starting temperature) and fast curing (total calorific value) are slightly inferior. This is a viscosity (catalog value) at 25 ° C of the glycidyl ether type epoxy compound (epolite 100 MF) used in Example 7 is 100? Although it was low at 160 mPa * s and the fluidity | liquidity in a capsule improved, the polymerization start temperature could be reduced, but the glycidyl ether type epoxy compound has cationic polymerization property compared with an alicyclic epoxy compound and an oxetane compound. It is because it is low.

Moreover, when the high boiling point lipophilic solvent used by normal interfacial superposition | polymerization is contained in the microcapsule from the result of the comparative example 2, it turns out that sufficient potential cannot be realized. This is considered to be because the capsule wall strength is lowered because interfacial polymerization in the microcapsules is inhibited.

Comparative Example 3 (In the case of containing oxetane compound, divinylbenzene and radical polymerization initiator)

The blending amount of the polyfunctional isocyanate is 50 parts by mass to 40 parts by mass, except that 10 parts by mass of divinylbenzene (Merck Co., Ltd.) and 0.1 parts by mass of a radical polymerization initiator (Ferroyl L, Nichi Oil Co., Ltd.) are newly added. And the operation of Example 3 were repeated to prepare the aluminum chelate latent curing agent of Comparative Example 3. In addition, a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

Comparative Example 4 (when oxetane compound, divinylbenzene and radical polymerization initiator are included)

The blending amount of polyfunctional isocyanate is 50 parts by mass to 30 parts by mass, except that 20 parts by mass of divinylbenzene (Merck Co., Ltd.) and 0.2 parts by mass of a radical polymerization initiator (Ferroyl L, Nichi Oil Co., Ltd.) are newly added. And the operation of Example 3 were repeated to prepare the aluminum chelate latent curing agent of Comparative Example 4. In addition, a thermosetting epoxy resin composition was prepared in the same manner as in Example 1.

<Evaluation of Comparative Examples 3 and 4>

The obtained thermosetting epoxy resin composition was thermally analyzed using a differential thermal analyzer (DSC) (DSC6200, Seiko Instruments). The obtained result is shown in Table 6 and FIG. For comparison, the result of Example 3 is also written together.

From Table 6 and FIG. 14, in Comparative Examples 3 and 4 in which the radically polymerizable compound was used in addition to the cationically polymerizable compound, both the exothermic onset temperature and the exothermic peak temperature shifted to the high temperature side, and further became broad peaks. It is considered that this is because the radical polymerization of the radically polymerizable compound occurs not only in the capsule surface but also in the capsule at the time of interfacial polymerization, so that a good core shell structure is not formed.

Industrial availability

The aluminum chelate latent curing agent of the present invention is inexpensive as an epoxy resin and can cure a general-purpose glycidyl ether type epoxy resin at low temperature in a short time. Therefore, it is useful as a hardening | curing agent of a general purpose epoxy resin composition.

Claims (15)

An aluminum chelate latent curing agent microencapsulated in a core-shell type, except that the radically polymerizable compound is contained in a capsule in which the aluminum chelate curing agent and the cationic polymerizable compound are composed of an interfacial polymer of a polyfunctional isocyanate. ) Aluminum chelate latent curing agent. The method of claim 1,
An aluminum chelate latent curing agent wherein the cation polymerizable compound is a cyclic ether compound. The method of claim 2,
An aluminum chelate latent curing agent wherein the cyclic ether compound is an alicyclic epoxy compound and / or an oxetane resin. The method according to any one of claims 1 to 3,
The aluminum chelate latent hardener which impregnated the aluminum chelate hardening | curing agent solution with respect to a capsule wall. The method according to any one of claims 1 to 4,
The cationically polymerizable compound is 10? To 100 parts by mass of the aluminum chelate-based curing agent. An aluminum chelate latent curing agent blended with 300 parts by mass. 6. The method according to any one of claims 1 to 5,
100 mass parts of aluminum chelate hardening | curing agents and a cationically polymerizable compound in 100 mass parts of capsule walls which consist of an interfacial polymer of polyfunctional isocyanate. An aluminum chelate latent curing agent containing 2000 parts by mass. A method for producing an aluminum chelate latent curing agent microencapsulated into a core-shell type according to claim 1, comprising an oil phase obtained by dissolving a polyfunctional isocyanate and a cationic polymerizable compound in a volatile organic solvent, containing water, a dispersant, and a surfactant. A polyfunctional isocyanate is interfacially polymerized while emulsifying in an aqueous phase, and the aluminum chelate hardening | curing agent and a cationic polymerizable compound are contained in the capsule which consists of an interfacial polymer of a polyfunctional isocyanate, The manufacturing method characterized by the above-mentioned. The method of claim 7, wherein
The blending ratio of the volatile organic solvent in the oil phase is 1? To 100 parts by mass in total of the aluminum chelate curing agent, the polyfunctional isocyanate, and the cationically polymerizable compound. 50 mass parts of manufacturing method. The aluminum chelate latent curing agent according to any one of claims 1 to 6, a glycidyl ether type epoxy compound, and formula (A)
(Ar) _m Si (OH) _n (A)
(Wherein m is 2 or 3, and the sum of m and n is 4, Ar is an aryl group which may be substituted)
The silanol compound represented by the thermosetting epoxy resin composition characterized by the above-mentioned. The method of claim 9,
The thermosetting epoxy resin composition whose silanol compound is triphenyl silanol or diphenyl silanol. The method according to claim 9 or 10,
The content ratio of the silanol compound to the total of the silanol compound and the glycidyl ether type epoxy compound is 5? A thermosetting epoxy resin composition which is 30 mass%. The method according to any one of claims 9 to 11,
A thermosetting epoxy resin composition wherein the glycidyl ether type epoxy compound is a bisphenol A type epoxy resin and / or a bisphenol F type epoxy resin. The method according to any one of claims 9 to 12,
Furthermore, the thermosetting epoxy resin composition containing an oxetane compound. The anisotropic conductive adhesive agent in which electroconductive particle is disperse | distributed in the thermosetting epoxy resin composition of any one of Claims 9-13. 15. The method of claim 14,
Anisotropic conductive adhesive molded into a film form.

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